JPS63156054A - Manufacture of polycomponent ceramics - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing multicomponent ceramics that are used in a wide range of fields as high-performance functional materials and structural ceramics.

[Prior Art] Ceramic sintered bodies are usually manufactured by mixing and pulverizing raw material powders, molding relatively large particle size powder (several microns), and firing the molded powder. For this reason, it has been difficult to obtain ceramics with high density and advanced functionality.

[Problems to be Solved by the Invention] This invention has been made in view of the above points, and it is possible to form a multi-component powder with particularly excellent sinterability and high bulk density.
Furthermore, it is an object of the present invention to provide a method for producing a high-performance, homogeneous, and high-density multicomponent ceramic material by firing this powder.

[Means for Solving the Problems] The method for producing multicomponent ceramics according to the present invention basically includes the following steps.

a) One component (x) constituting the multicomponent ceramic compound
suitability Q(Y) of at least one component other than
A mixed solution with the solution of b) the ☆ powder made of this calcined product, the remaining constituent parts of the desired multi-component ceramic composition, and the remainder of at least one of the above components (Y); Mix with 50 minutes
a step of calcining at 0 to 1300°C; c) molding the calcined powder obtained in step lx;
It consists of a step of firing at 2000°C.

In this invention, the particle size of the particles obtained in step a) is preferably in the range of 0.01 to 0.06.

The calcination temperature of the precipitate or precipitate obtained in this invention is 700 to 1300°C.

If the temperature is lower than 700°C, it tends to aggregate, and if it exceeds 1300°C, the particles become coarse. In addition, the precipitate or Oi product was
As in Yuki, after calcination, another component is mixed and this mixture is calcined, but at the lowest temperature tool 1- where the in-phase reaction is almost or completely completed, significant particle growth also occurs. It is necessary that the maximum temperature is within the range of 500~
A range of 1300°C is preferable. The calcined product made in this way is 70
It is fired at a temperature of 0 to 2,000°C, but if it is lower than 700°C, the entire firing will be insufficient, and if it exceeds 2,000°C, the particles will increase in size or the constituent components will volatilize.

[Operation] In the step a) above, the particle size is 0.01 to 1.0 μm.
In the step b), the powder is submicron-sized and has a good degree of mixing of components, and the desired component composition is obtained in step b).

Therefore, by further adding a residual component to this powder, a powder having powder properties that maintains the above characteristics a) can be produced. For this reason, rather than producing a multicomponent ceramic of the desired composition only in step a), -
Since the shell powder raw material is used, it can be manufactured at a sufficiently low cost. In addition, since low temperature firing is possible, high quality ceramics with high firing density can be obtained.

[Example 1] Titanium tetrachloride aqueous solution (1,3317)/mol concentration) 4
3.57cc and zirconium oxynitrate aqueous solution (1,1
46j! /1Iol concentrated) 150cc were mixed. This mixed aqueous solution was gradually added to 1 volume of stirring 6N-ammonium water to prepare hydroxides of Ti4+ and Zr' (
A precipitate was obtained. This was washed, dried, and then calcined at 1100°C (T 10.2Zro, g) to produce 02 powder.

The average particle size of this powder was 0.32 μm.

3.5779 g of the powder thus obtained, 1.4981 g of T i 02 fine powder sold by RLJ, and PbO powder ('
After mixing 11.16 g of P (average particle size 15 μm) in a ball mill for a day and night, the mixture was calcined at 740°C for 1 hour to obtain Pb (Z
r-TI)03 powder was obtained. So0.5 0.
The average particle size of No. 5 was 0.32 μm. This calcined powder is 1
It is molded at t/cI2 to form a tablet, and this tablet is molded at 12 m in an atmosphere where lead vapor and oxidizing gas coexist.
Sintering was performed at 20°C for 1 hour. The density of this sintered tablet reaches 7.95, which is very close to the theoretical density.

The composition produced in this example is represented by the general formula ABO3, and the A component (oxygen 12-coordinated metal element) of this perovskite compound is, for example, P b s B
Examples include rare earth elements such as a SCa S r and La. In addition to zirconium, the B component (oxygen hexacoordination metal element) includes, for example, Ti5Mg5Sc%
Hf, Th%W1N b s Ta −, Cr, Mo
, Mn5Fe, , CosN l % Cd % A 1
% S n SA s s B and the like.

Note that the present invention also includes those in which the molar ratio of component A and component B is shifted to a value higher or lower than 1.0.

Furthermore, in order to improve the sinterability and properties of perovskite-based functional ceramics, it is customary to add a small amount of auxiliary agents, and these auxiliary agents are added in the first or second stage of the process. Just add it appropriately.

Compounds for making zirconium solutions (aqueous or alcoholic solutions) include zirconium oxychloride,
Mention may be made of zirconium oxynitrate, zirconium chloride, zirconium nitrate and zirconium metal.

Examples of reagents for preparing the precipitate-forming solution include organic reagents such as ammonia, ammonium carbonate, caustic alkali, oxalic acid, ammonium oxalate, amines, and oxine.

The types and amounts of perovskite components dissolved in the zirconium solution are those that can suppress agglomeration of the zirconia powder that is finally obtained by adding the components, and those that are commonly included in perovskite functional ceramics. It is preferable. When the calcination temperature of the obtained coprecipitate is 700 to 1300°C, a good sintered body can be obtained, and a powder of 0.01 to 1.0 μm can be obtained.

When the temperature is lower than 700°C, significant aggregation occurs, and when the temperature exceeds 1300°C, the particles tend to become coarse. To the thus obtained mixture, the remaining components other than zirconium are added and mixed. Of course, it is also necessary to replenish any missing ingredients added to zirconia. In this case, the particle size of any compound powder (mainly oxide) used is submicron grade. However, even if coarse lead oxide powder is used, it has little effect on the properties of the resulting perovskite powder.

The calcination temperature of these mixtures is
500 in cases containing “Nb and Ta”.
It varies significantly in the range of ~1300°C. In short, the temperature needs to be higher than the minimum temperature at which the solid phase reaction is almost or completely completed, and within the maximum temperature range at which significant particle growth does not occur.

The powder thus obtained is shaped and sintered. The sintering temperature, like the calcination temperature of the mixture described above, varies depending on the types of constituent components, but is generally in the range of 700 to 1700°C. If the temperature is lower than 700°C, even perovskite containing PB will not be sintered sufficiently, and if the temperature exceeds 1700°C, the particles will become coarse or the constituent components will volatilize.

[Example 2] An experiment was conducted using the same steps as in Example 1, but only changing the calcination temperature of the hydroxide coprecipitate.

The drawings show the average particle size (according to SEM observation) of the calcined product calcined at 700 to 1300°C and the density of the sintered body obtained by firing at 1220°C for 1 hour.

[Example 3] Titanium tetrachloride aqueous solution (1,3317)/l1ol@degree)
43.57cc and zirconium oxychloride aqueous solution (1,
146,+? /sol 8 degrees) and 150 cc. This mixed aqueous solution was maintained at 100° C. for 100 hours to carry out a hydrolysis reaction to obtain a sol containing T14+ and 24+. After washing and drying this sol, 1100℃
< T + o, 2Z ro, g) 02 powder was prepared by calcining at <T+o, 2Z ro, g).

The average particle size of this powder was 0.32 μm.

3.5779 g of this calcined powder, 1.4981 g of commercially available T i O2 fine powder, and PbO powder (average particle size 15 μm) 1
After mixing 1.16g in a ball mill for a day and night, 74g
Pb (Zr -Ti
)03 powder was obtained. Part 1'.

0.5 0.5 The average particle size was 0.32 μm. and add this powder to it
/ca+2 to form a tablet, and the tablet was heated at 1220°C in an atmosphere coexisting with lead vapor and oxygen gas.
It was sintered for 1 hour. The density of the obtained product reaches 7.95, which is very close to the theoretical density.

[Comparative Example 1 (compared to Examples 1 to 3) Commercially available PbO
, TiO2, ZrO2 powder in pb (Zr ・Tio,
5) The mixture was blended to have a composition of 0.5 and mixed in a ball mill for one day and night, and then calcined at 850° C. for 2 hours. This powder was compacted at it/d and sintered under the same conditions as in Example 1.

The density of the obtained ceramic was about 6.5. Note that the average particle size of the powder at the time of calcination was 2.3 μm.

[Example 4] Ferric nitrate aqueous solution (1.5 J!/mol solution) 225c
c and 180 cc of sodium niobate aqueous solution (1,2)/mol solution) were mixed.

6N-ammonia water 11 stirring this mixed aqueous solution
! was added gradually to obtain a hydroxylated coprecipitate of Fe3+ and Nb5+. This was washed, dried, and then calcined at 700°C to produce FeNb0t powder.

Then, 1.0 g of commercially available Fe2O3 was added to 10 g of this calcined powder.
349g, WO3 1.964g5Pb0 28.34
After mixing with 6g in a ball mill for a day and night, 1
After time calcination, the thickness is 0.3 μm. This powder was molded at 0.7Loa+/co+2 and heated to 8
It was baked at 70°C for 1 hour. The density at this time was 8.1 g/am3, the dielectric constant at I KHz, and the dielectric loss were εr-10200 and tan δ-2%.

Further, the specific resistance was 1.11010 Ω·elm, and a good material was obtained.

[Example 5] 16.23 g of ferric chloride and 27.04 g of niobium pentachloride were dissolved in 1 liter of water to obtain a mixed solution.
It was kept at 0°C for 90 hours. As a result, a hydrolysis reaction was carried out to obtain a sol containing Fe3+ and NbS+. After washing and drying this, it is calcined at 700°C to obtain F e N b
O4 powder was produced. Commercially available Fe2 is added to 10g of this powder.
1.349g O3% 1.96g WO3.

After mixing 28.35 g of pbo in a ball mill overnight, the mixture was calcined at 700°C for 1 hour to obtain 0.8Pb03 powder. Its particle size is 0.25°C μm. Then, this calcined powder was molded at 0.7 ton/d and fired at 870° C. for 1 hour in a hot pot.

The density at this time is 8.22 g/am3, IK
The dielectric constant and dielectric loss at Hz were εr-10000° tan δ-1.5%. Also, the specific resistance is 1.2X
I Q I OΩ・el, indicating a good key material.

[Comparative Example 2] Commercially available P b (relative to Example 4.5)
OSF e203 and Nb205 were weighed, and 100 g of the weighed powder was mixed in a ball mill for a day and night, and then calcined at 700° C. for 1 hour to obtain a powder of 1.5 μm. This was press-molded in the same manner as in the example and fired at 870°C for 1 hour. In this case, the bulk specific gravity is 7.1g/en+3
It showed low values of er-5400, tan δ-1096, and specific resistance of 7×107Ω and Ca. Further, the firing temperature at which the density of this material reached its maximum was 980°C, which was 110°C higher than that of the example.

[Example 6] This example is (Z r, 8S n, 2) T t 04
43.57 cc of titanium tetrachloride aqueous solution (1,3' 17 f/mol concentration) and 150 cc of zirconium oxynitrate aqueous solution (1,146 j?/mol concentration) were mixed. This mixed aqueous solution was added to a 6N ammonia aqueous solution to obtain a coprecipitate containing Ti4+ and Zr'.

After washing and drying this, it was calcined at 1100℃ (Z r
o, gT 1o4) Created 02 Song Song.

The average particle size of this powder was 0.32 μm.

3.5779 g of this calcined powder and 1 commercially available TiO□ fine powder
．． 9963g, 5n024.7065g (Z r
o, 8S n, 2) T t O4 The mixture was mixed overnight in a ball mill, and then calcined at 1000°C for 1 hour (Z r, 8S n, 2) T i 0
4 powders were obtained. The particle size was approximately 0.36 μm. Then, this powder was formed into a tablet at 1 ton/ci, and the tablet was fired at 1450° C. for 2 hours in the air. The properties of the tablet thus obtained are that the density is 4.94 g.
/ccεr-36.0, and the Q value was 5,500.

[Example 7] This example is (Z r□, gS no, 2) T i
Regarding Oa, titanium tetrachloride aqueous solution (1,331
7)/l101 concentration) 43.57cc and zirconium oxychloride water dissolution (1,146, ff/sol concentration) 15
0cc was mixed. This mixed aqueous solution was heated to 100°C for 10
A hydrolysis reaction is carried out by holding for 0 hours, and T
A sol containing i4+ and Zr' was obtained. After washing and drying this, it was calcined at 1100℃ (Z ro, aT t, 2
) 02 powder was produced.

The average particle size of this powder was 0.28 μm.

3.5779 g of this calcined powder is also commercially available TiO2 fine powder 1
．． 9963g5Sn024.7065g (Z r,
8Sn, 2) T i O4 powder was mixed in a ball mill for a day and night, and then calcined for 1 hour at 1000° C. to obtain (Zr0.8Sno, 2) T i 04 powder. The particle size of this powder was approximately 0.33 μm. Then, this powder was molded into tablets at 1 ton/d.
This tablet was fired at 1450° C. for 2 hours in the atmosphere.

The properties of the obtained product were a density of 4.97 g/cc.

εr-37.0, Q value: 6000.

[Comparative Example 3] As a comparative example (relative to Example 6.7), commercially available Z ro2.5n02, TiO2 powder (Zr0
．． 8Sno, 2) Zr0 to have a composition of Ti04
2-9.857g.

5n02-3.014g and TiO27,990g were mixed in a ball mill for one day and night, and then calcined at 1000°C for 1 hour. The particle size of the calcined powder was 2.1 μm, and the culmability was 2.1 μm.

This powder was molded at 1 ton/cIj and fired under the same conditions as in the example. Its characteristics are density 4.22g/cc,
εr-27.2, Q value: 2000.

[Example 8] Tetraisopropoxy titanium [T i (iso-0C3Hy) 4 ] l
l1ol and tetraethoxysilane [S i (OC
2H5) 4] 1 mol and 1.2I! A mixed solution of ethanol [C2H50H] is prepared, and while stirring this mixed solution, 6N hydrochloric acid 80WII! drip,
A silica titania sol solution was prepared by hydrolysis. This sol solution was mixed with 6N ammonia water while stirring. i?
Ti4+ and S were gradually added at a rate of 150cc into
A hydroxide coprecipitate of i4+ was obtained. After washing and drying this, a reduction nitriding treatment was performed for 10 hours in an ammonia stream at 1100° C. to obtain a calcined nitride. The grain size of this calcined nitride was 0.1 to 0.3 μm.

Next, the two-legged calcined nitride was further added with an average tel diameter of 0.8.
Micron silicon nitride (Si3N4) powder was mixed with 0.411 Iol and spinel (MgA) was used as a sintering aid.
1204) 0.04mol, yttrium oxide (
Y203) 0.025 aol was mixed.

This mixed powder is mixed with a solvent and a binder to form a slurry, which is molded into a predetermined shape taking into account the shrinkage rate, degreased at 360°C, and then heated to 175°C.
Firing was performed at 0° C. for 4 hours in a nitrogen atmosphere. After that, the surface of the sintered body is polished to obtain a test piece with the required dimensions. 17.

[Example 9] Tetraisopropoxy titanium [T i (lso -0C3H7) 4 ] 1a
+ol and tetraethoxysilane [Si (oC2H5
)4] and 1, =I! of ethanol [C2H50
A mixed solution of H] was prepared. While stirring this mixed solution, 80 mL of 6N hydrochloric acid was added dropwise to hydrolyze it, and the silica titania sol solution was prepared once. This was gelatinized at 50°C and dried for 30 hours. The silica-titania gel thus obtained was subjected to photo-nitriding treatment for 10 hours in an ammonia stream at 1100"C to obtain a calcined nitride. The particle size of this calcined nitride was 0.05~ It was 0.3 um.

Next, 0.411% of silicon nitride (Si3N4) powder with an average particle size of 0.8 μm was added to the above calcined nitride.
Iol and spinel (MgA 120+) as a sintering aid.
)0.04sol, yttrium oxide (Y203
) 0. 025101 was mixed.

This mixed powder is mixed with an organic solvent as a solvent and a binder to form a slurry, which is molded into a predetermined shape considering the shrinkage rate, degreased at 360"C, and then heated to 1750"C.
Firing was performed at ℃ for 4 hours in a nitrogen atmosphere. After that, the surface of the sintered body was polished and a test piece of the required size was obtained.

[Comparative Example 4] In this example (compared to Example 8.9), as a result of analyzing the component ratio of TiN and Si3N4 in the final sintered body, the molar ratio of TiN: Si3 N4 = 5
7.5:42.5, but for comparison, a comparative test piece was prepared using the following method so as to have the same composition using a normal method.

・Silicon nitride with a uniform particle size of 0.8 μm, ・A uniform particle size of 0.5
The required amount of titanium nitride is weighed and the silicon nitride is 41 m
ol 96, titanium nitride 55.4% a+o1%, this mixed powder also contained MgA 1%.
2042. 211101%, Y2O31,4ao1%
sintering aid is mixed.

This mixed powder is mixed with an organic solvent as a solvent and a binder to form a slurry, which is molded into a predetermined shape considering the shrinkage rate, degreased at 360°C, and then heated to 175°C.
Firing was performed at 0° C. for 4 hours in a nitrogen atmosphere (−).The surface of the sintered body was then polished to obtain a comparative test of required dimensions.

1st] Particle size of the modified composition in step 2: 0.01 to 1.0 μm
Examples 1.2 and 3゜5.8 show a neutralization coprecipitation method, and Examples 3 and 5゜7.9 show a hydrolysis method of an aqueous chloride solution and an alkoxide mixed solution. There is.

Other hydrothermal hydrolysis methods at high temperatures (120 to 200 degrees Celsius) and high pressures (several atmospheres), alkoxide hydrolysis methods, and metal powder
0 atm) method to obtain fine oxide powder, and the method to obtain powder by evaporating a mixed solution of metal salts etc. to dryness and thermally decomposing it at high temperature (this specific example). Methods include spray drying, freeze drying, automatic fiber impregnation pyrolysis, alkoxide pyrolysis).Furthermore, gas phase methods in a vacuum container are also available. This method is suitable for manufacturing.

[Other Examples] In other multi-component compositions as described above, high densities were achieved in the same manner as in the above examples, and improvements in various properties were obtained accordingly.

Piezoelectric porcelain 0.8Pb (TlyZry) O・-〇・2Pb (Mgy
3N-)0.0.8Pb(TlyZry)O.-0
・2Pb (Yy2Nb3/2) 0 ・Transparent porcelain 0.022 (Pb La )"0.978 (Z
r, 65Tl, 35) 00.91 0.09 0.022 (Pb Ba )'0.978 (Z
ro, 53Tl, 47) 00.95 0.05 0.022(PbSr)-0,978(Z
ro, 53Tl, 4 guns) OQ, 95 0.05 0.022 (Pb old) ・0.978 (
Zr, 65T! , 35) 00.91 0.09 0.022 (Pb 1.a) ・0.97
8 (111', 65Tlo, 35) 00.91 0.0
9 Antiferroelectric PbZrO3 Semiconductor capacitor (S B C) Ti03 (x+y+z=1)r
X ag az resonator porcelain (SrO, 73BaO, 27) (Z'O, Q73 (
1,027) 0゜Ti Ha (Zno, aaNbo, 53TaO, t
3) o38''(Zn'/3Nb3□ゝ 0. Ba Ti 40s PTC porcelain (BaO, 999Yo, oot) TI O3 magnetic material Bad, 6Fe20j+3mo1%Zr02NjO-F
e203 Low expansion material ZrT'i04 Alumina porcelain 0.8AJ O-0,2 (0,95ZrO-0,05
YO) 0.98 AiO-0,02(3Y 0
・5AiO) Zirconia porcelain 0.95Zr02 o, 05Y203 Conductive material 0.27TiN-0,73AIN Conductive material 0.25TiC-0,75SiC Substrate 0.975AIN-0,025Y203 Substrate 0.975AI! N -0,025Y 2030.51
AI! 203 0.35S i O20,14Pb
O

[Brief explanation of the drawing]

The attached drawing is a diagram showing the relationship between the 9i calcination temperature of the calcined material obtained in Example 2 of the present invention, and the particle size and density of the calcined material. Applicant's agent Patent attorney 1. Takeshi Suzue α type 1-b copper
3

Claims (1)

[Claims] One component (X) constituting a multicomponent ceramic compound
an appropriate amount of at least one component other than (Y), and one component (X
), from this mixed solution a precipitate or precipitate containing each of the above components is formed, and this precipitate or precipitate is calcined at 700 to 1300°C to obtain a particle size of 0.0
a first step of forming a fine powder that becomes a modified powder of 1 to 1.0 μm; the modified powder obtained in the above step; the remaining components of the desired multicomponent ceramic composition; and at least one of the above components. Mix with the appropriate amount (Y) of the remainder and heat at 500 to 1300°C.
and a third step of forming a calcined powder from the calcined product obtained in the second step and firing it at 700 to 2000°C. Method for producing multicomponent ceramics.